DE60215218T2 - MILKY ACID POLYMER COMPOSITION AND FORM BODY THEREOF - Google Patents

Abstract

Disclosed herein are a lactic acid-based polymer composition comprising: (i) an amide compound represented by General Formula (1): <CHEM> wherein R<1> represents a C2-30 saturated or unsaturated aliphatic polycarboxylic acid residue, a C4-28 saturated or unsaturated alicyclic polycarboxylic acid residue, or a C6-28 aromatic polycarboxylic acid residue, and R<2> represents C1-18 alkyl, C2-18 alkenyl, C3-12 cycloalkyl or cycloalkenyl or the like, (ii) an ester plasticizer, and (iii) a lactic acid-based polymer; a transparent, crystalline (heat resistant) molded article molded from such a lactic acid-based polymer composition; and a method for producing such a molded article.

Description

TECHNICAL AREA

The The present invention relates to a lactic acid-based polymer composition, comprising a lactic acid-based polymer and a shaped body from lactic acid-based polymer, by molding such a lactic acid-based polymer composition will be produced.

BACKGROUND OF THE INVENTION

In In recent years, processes for the disposal of polyethylene, Polypropylene, polystyrene, polyvinyl chloride and corresponding typically used plastics, which does not decompose in the natural environment become a problem in terms of environmental protection. The most of these conventionally Used plastics are made by incineration or landfill disposed of without reuse or recycling. polyethylene, But polypropylene and polystyrene have a high heat of combustion and if this conventionally used plastics are likely to damage incinerators. It is also known that the combustion of polyvinyl chloride toxic gases such as dioxins and the like produced. In landfilling, these are conventionally used Plastics are chemically stable and remain almost permanent, which is the Problem of landfill scarcity aggravated.

To solve these problems, biodegradable polymers and articles formed therefrom are required, which decompose in a natural environment. Accordingly, active research efforts have been made to develop naturally decomposable aliphatic polyester resins such as copolymers of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, polycaprolactone, polybutylene succinate, etc. Polylactic acid and the copolymers thereof are an example of these resins. Lactic acid-based polymers are biodegradable and have a low heat of combustion, one-third to one-half that of polyethylene and polypropylene, and does not cause damage to incinerators. Moreover, when burned, lactic acid-based polymers do not produce toxic gases such as hydrogen chloride, NO _x , SO _x, and especially dioxins. In addition, lactic acid-based polymers are expected to be able to replace commonly used plastics, since lactic acid-based polymers can be made from plant sources of starting material (cornstarch, etc.) which are renewable annually, thereby increasing their use petroleum or similar fossil sources.

With rapid technical development in the field of electronic, mechatronic and optoelectronic devices, lasers, liquid crystals, the optical devices office automation, factory automation, etc., is the need for transparent foils have risen rapidly and their applications have also widened rapidly. Examples of special applications of transparent films include overhead projector transparencies, plate making films, Pausfilme, films for food wrapping, agricultural Films, transparent electrically conductive films (e.g., for touch-sensitive Fields for Computer input, etc.), heat reflective films, liquid crystal display films, liquid crystal display polarizing films, Printed circuit boards etc.

Even though Glass, acrylic (e.g., polymethyl methacrylate), polycarbonate, and the like rigid films of low flexibility have hitherto been used for these applications Recently, they have been rapidly becoming transparent Films with high flexibility, Formability, heat resistance and corresponding properties have been replaced. polyethylene terephthalate (PET) films can as an alternative for these slides are used. But PET gives a problem in applications where biodegradability or decomposability in natural Environment is required. With regard to the above Background is therefore predicted that the influence of slides with transparency, heat resistance (Crystallinity) and decomposability in the technical field of transparent Slides will be significant.

Molded lactic acid-based polymers which are degradable thermoplastic polymers such as polylactic acid or copolymers of lactic acid and one or more compounds having two or more functional groups capable of forming an ester linkage (eg, aliphatic hydroxycarboxylic acids, lactones, etc.) usually amorphous and transparent immediately after molding since they do not contain crystals which are of a size or size greater than the wavelength of the light, thereby causing light scattering. Molded bodies obtainable from such lactic acid-based polymers, however, are usually poor in heat resistance because of their amorphous nature. Thus, for example, containers of amorphous polylactic acid are superior in transparency, but are inferior in heat resistance and therefore can not be contacted with hot water or can not be used in applications where they are to be heated in microwave ovens, and their applications have been limited.

to Improvement of heat resistance become shaped bodies of polymer based on lactic acid heat treatments subjected to them during of the molding process be kept in a mold for a long period of time at a temperature in the vicinity their crystallization temperature is maintained, or amorphous moldings directly be tempered after forming. As crystallization progresses but crystals (e.g., spherulites) grow rapidly with a similar one or larger size than that wavelength of light, which causes light scattering to crystals with one To give greatness, which the wavelength of visible light, with the result that the resulting moldings become opaque.

• 1) Es ist offenbart, dass Formkörper aus aliphatischem Polyester, die sowohl Transparenz als auch Kristallinität aufweisen, durch Zugabe eines aliphatischen Carboxylamids mit einem Schmelzpunkt von 40 bis 300°C in einer Menge von 0,1 bis 10 Gew.-Teilen zu einem aliphatischen Polyester wie Polymilchsäure hergestellt werden. Obwohl diese Technik dadurch gekennzeichnet ist, dass eine Wärmebehandlung während oder nach der Formgebung durchgeführt wird, um die Kristallinität unter normalen Formbedingungen zu erhöhen, offenbaren die Arbeits beispiele nur, dass die Wärmebehandlung nach der Formgebung durchgeführt wird. Dieses Verfahren ist nicht notwendigerweise ein industriell vorteilhaftes Verfahren, da ein solcher Wärmebehandlungsschritt nach der Formung erforderlich ist und Formkörper bei Fortschreiten der Kristallisation während der Wärmebehandlung sehr verformt werden (ungeprüfte JP-Patentveröffentlichung Nr. 278991-1997).
• 2) Es wird eine Technik offenbart, bei der eine Amidverbindung mit einer bestimmten Struktur zu einem Polymilchsäureharz zugegeben wird, um die Kristallinität des Polymilchsäureharzes zu erhöhen und dadurch die Ablösbarkeit vom Formwerkzeug zu verbessern. Obwohl die Arbeitsbeispiele die Verbesserung der Ablösbarkeit vom Formwerkzeug zeigen, wird die gleichzeitige Anwesenheit von Transparenz und Kristallinität nicht erörtert (ungeprüfte JP-Patentveröffentlichung Nr. 87975-1998).

In the technical field of lactic acid-based polymers, there are disclosed techniques in which an additive or a nucleating agent, which will be described later, is added to inhibit spherulite growth to give transparency or to improve the rate of crystallization, thereby enhancing crystallinity to increase. In industrial terms, however, this effect is not necessarily sufficient.

• 1) It is disclosed that molded articles of aliphatic polyester having both transparency and crystallinity by adding an aliphatic carboxamide having a melting point of 40 to 300 ° C in an amount of 0.1 to 10 parts by weight to an aliphatic Polyesters such as polylactic acid are produced. Although this technique is characterized in that a heat treatment is performed during or after the molding to increase the crystallinity under normal molding conditions, the working examples merely disclose that the heat treatment is performed after the molding. This method is not necessarily an industrially advantageous method because such a heat treatment step after molding is required and moldings are much deformed as the crystallization proceeds during the heat treatment (Japanese Unexamined Patent Publication No. 278991-1997).
• 2) There is disclosed a technique in which an amide compound having a specific structure is added to a polylactic acid resin to increase the crystallinity of the polylactic acid resin and thereby improve mold releasability. Although the working examples show the improvement of releasability from the mold, the simultaneous presence of transparency and crystallinity is not discussed (Japanese Unexamined Patent Publication No. 87975-1998).

in view of it is the techniques disclosed in the above references currently industrially difficult, moldings of polymers based on lactic acid at the same time to give transparency and crystallinity.

EPIPHANY THE INVENTION

One The aim of the present invention is to provide a polymer composition based on lactic acid, which is capable of forming a shaped body with transparency and with crystallinity (heat resistance) to form, and one Molding, by molding such a lactic acid-based polymer composition will be produced.

• 1) Während (oder nach) der Formgebung einer Polymerzusammensetzung auf Milchsäurebasis, die durch Zugabe einer bestimmten Amidverbindung und eines bestimmten Esterweichmachers zu einem Polymer auf Milchsäurebasis hergestellt wird, wirken, wenn ein Kristallisierschritt des Polymers auf Milchsäurebasis durchgeführt wird, die Amidverbindung und der Esterweichmacher synergistisch, wodurch ein Gegenstand mit Transparenz und Kristallinität (Wärmebeständigkeit) gebildet wird.
• 2) Der Formgebungszyklus kann durch Erhöhung der Kristallisationsgeschwindigkeit im oben genannten Kristallisationsschritt verkürzt werden.

The inventors have conducted extensive research to achieve the above object and found that:

• 1) During (or after) the molding of a lactic acid-based polymer composition prepared by adding a certain amide compound and a certain ester plasticizer to a lactic acid-based polymer, when a crystallizing step of the lactic acid-based polymer is performed, the amide compound and the ester plasticizer act synergistically , whereby an article with transparency and crystallinity (heat resistance) is formed.
• 2) The molding cycle can be shortened by increasing the crystallization rate in the above-mentioned crystallization step.

The The present invention has been made by conducting further research Based on these findings.

worin R³ C_1-18-, insbesondere C_1-4-Alkyl, C_2-18-, insbesondere C_4-10-Alkenyl, C_1-18-, insbesondere C_1-4-Alkoxy, C_3-18-, insbesondere C_5-12-Cycloalkyl, Phenyl, oder Halogen ist; R⁴ lineares oder verzweigtes C_1-4-Alkylen ist; R⁵ und R⁶ die gleiche Bedeutung wie R³ haben; R⁷ die gleiche Bedeutung wie R⁴ hat; und R⁸ die gleiche Bedeutung wie R³ hat;
a eine ganze Zahl von 2 bis 6, insbesondere 2 bis 4 ist; b eine ganze Zahl von 1 bis 5, insbesondere 1 bis 3 ist; c eine ganze Zahl von 0 bis 5, insbesondere 0 bis 3 ist; d eine ganze Zahl von 1 bis 5, insbesondere 1 bis 3 ist; und e eine ganze Zahl von 0 bis 5, insbesondere 0 bis 3 ist;
(ii) mindestens einen Ester-Weichmacher; und
(iii) ein Polymer auf Milchsäurebasis.Item 1. A lactic acid-based polymer composition comprising:
(i) at least one amide compound represented by the general formula (1): R ¹ - (- CONHR ² ) _a (1) wherein R ^{1 is} a saturated or unsaturated C _2-30 aliphatic polycarboxylic acid residue, especially C _4-10 polycarboxylic acid residue, a saturated or unsaturated C _4-28 alicyclic polycarboxylic acid residue, especially C _5-10 polycarboxylic acid residue, or an aromatic C _6-28 Polycarboxylic acid residue, especially C _6-12 polycarboxylic acid residue;
R ^{2 is} C _1-18 , especially C _4-10 alkyl, C _2-18 , especially C _4-10 alkenyl, C _3-12 , in particular C _5-8 cycloalkyl or cycloalkenyl, phenyl, naphthyl , Anthryl, or a group represented by the general formula (a), the general formula (b), the general formula (c) or the general formula (d);

in which R ^{3 is} C _1-18 -, in particular C _1-4 -alkyl, C _2-18 -, in particular C _4-10 -alkenyl, C _1-18 -, in particular C _1-4 -alkoxy, C _3-18 - , in particular C _5-12 -cycloalkyl, phenyl, or halogen; R ^{4 is} linear or branched C _1-4 alkylene; R ⁵ and R ^{6 have} the same meaning as R ³ ; R ^{7 has} the same meaning as R ⁴ ; and R ^{8 has} the same meaning as R ³ ;
a is an integer from 2 to 6, especially 2 to 4; b is an integer from 1 to 5, especially 1 to 3; c is an integer of 0 to 5, especially 0 to 3; d is an integer from 1 to 5, especially 1 to 3; and e is an integer of 0 to 5, especially 0 to 3;
(ii) at least one ester plasticizer; and
(iii) a lactic acid-based polymer.

Item 2. A lactic acid-based polymer composition according to item 1, wherein R ^{1 is} a 1,4-cyclohexanedicarboxylic acid residue, a 2,6-naphthalenedicarboxylic acid residue, a trimesic acid residue or a 1,2,3,4-butanetetracarboxylic acid residue.

Item 3. A lactic acid-based polymer composition according to item 1, wherein R ^{1 is} a trimesic acid residue.

Item 4. A lactic acid-based polymer composition according to item 1, wherein R ^{1 is} a 1,4-cyclohexanedicarboxylic acid residue, a 2,6-naphthalenedicarboxylic acid residue, a trimesic acid residue or a 1,2,3,4-butanetetracarboxylic acid residue and R ^{2 is} tert-butyl, Cyclohexyl, phenyl, 2-methylcyclohexyl, 4-methylcyclohexyl or benzyl.

Point 5. A lactic acid-based polymer composition according to item 4, wherein the amide compound comprises at least one member selected from the group from trimesic acid tricyclohexylamide, Trimesinsäuretri (2-methylcyclohexylamide), Trimesinsäuretri (4-methylcyclohexylamide), 1,4-Cyclohexandicarbonsäuredicyclohexylamid, 1,4-Cyclohexandicarbonsäuredi (2-methylcyclohexylamide), 1,4-Cyclohexandicarbonsäuredibenzylamid, 2,6-Naphthalindicarbonsäuredicyclohexylamid, 1,2,3,4-Butantetracarbonsäuretetracyclohexylamid and 1,2,3,4-butanetetracarboxylic acid tetraanilide is.

Point 6. A lactic acid-based polymer composition according to any one of Items 1 to 5, wherein the ester plasticizer is at least one element selected from the group consisting of polyhydric alcohol derivatives, hydroxycarboxylic acid derivatives, aliphatic or aromatic carboxylic acid esters, polyether polyol derivatives and phosphoric acid derivatives is.

Point 7. A lactic acid-based polymer composition according to item 6, wherein the ester plasticizer comprises at least one element selected from the group consisting of glycerol derivatives, citric acid derivatives and polyalkylene glycol derivatives.

Item 8. A lactic acid-based polymer composition according to item 7, wherein the glycerin derivative is at least one aliphatic glyceric acid triester (aliphatic acid: C _2-18 ).

Point A polymer composition based on lactic acid according to item 7, wherein the citric acid derivative, at least one element selected from the group consisting of Acetylcitronensäuretrialkylestern 9 (alkyl: C _1-18) and citrates (alkyl: C _1-18), respectively.

Item 10. A lactic acid-based polymer composition according to item 7, wherein the polyalkylene glycol derivatives have at least one member selected from the group consisting of diethylene glycol di-aliphatic carboxylic acid esters (aliphatic carboxylic acid: C _2-18 ), triethylene glycol di-aliphatic carboxylic acid esters (aliphatic carboxylic acid : C _2-18 ), tetraethylene glycol di-aliphatic carboxylic acid esters (aliphatic carboxylic acid: C _2-18 ), polyethylene glycol di-aliphatic carboxylic acid esters (aliphatic carboxylic acid: C _2-18 ), diethylene glycol di-aromatic carboxylic acid esters, triethylene glycol di-aromatic-carboxylic acid esters, tetraethylene glycol-di-aromatic-carboxylic acid esters, polyethylene glycol-di-aromatic-carboxylic acid esters, dipropylene glycol-di-aliphatic-carboxylic acid esters (aliphatic carboxylic acid: C _2-18 ), tripropylene glycol-di-aliphatic-carboxylic acid esters (aliphatic carboxylic acid : C _2-18 ), tetra-propylene glycol-di-aliphatic-carboxylic acid esters (aliphatic carboxylic acid: C _2-18 ), polypropylene glycol di-aliphatic carboxylic acid esters (aliphatic carboxylic acid: C _2-18 ), dipropylene glycol di-aromatic carboxylic acid esters, tripropylene glycol di-aromatic carboxylic acid esters, tetrapropylene glycol di-aromatic carboxylic acid esters, and polypropylene glycol di-aromatic-carbonsäureestern.

Point 11. A lactic acid-based polymer composition according to any one of Items 1 to 10, wherein the lactic acid-based polymer is a weight average of the molecular weight of 50,000 or more.

Point 12. A lactic acid-based polymer composition according to any one of Items 1 to 11, which contain 0.01 to 10 parts by weight of the amide compound and 1 to 300 parts by weight of the ester plasticizer per 100 parts by weight of the lactic acid-based polymer includes.

Point 13. A shaped body, prepared by molding the lactic acid-based polymer composition according to any one of items 1 to 12.

Point 14. A shaped body, prepared by molding the lactic acid-based polymer composition according to any one of items 1 to 12, wherein the shaped body has a Degree of crystallization of 30% or more and transparency accordingly a cloudiness of 70% or less at a thickness of 0.5 mm.

• (1) Einfüllen einer Schmelze der Polymerzusammensetzung auf Milchsäurebasis in Form von Pellets in ein Formwerkzeug und Kristallisieren der Schmelze im Formwerkzeug; oder
• (2) Extrudieren einer Schmelze der Polymerzusammensetzung auf Milchsäurebasis in Form von Pellets aus einem Extruder mit T-Düse und Kristallisieren der Schmelze mit einer Kühlwalze;

wobei die Schmelze bei einer Temperatur im Bereich von Tc bis Tg kristallisiert wird, wobei Tc die Temperatur des Kristallisationsbeginns der Polymerzusammensetzung auf Milchsäurebasis und Tg die Glasübergangstemperatur der Polymerzusammensetzung auf Milchsäurebasis gemessen mit einem Differentialscanningkalorimeter ist.Item 15. A process for producing the molded article from the lactic acid-based polymer of item 14, the process comprising:

• (1) filling a melt of the lactic acid-based polymer composition in the form of pellets into a mold and crystallizing the melt in the mold; or
• (2) extruding a melt of the lactic acid-based polymer composition in the form of pellets from a T-die extruder and crystallizing the melt with a chill roll;

wherein the melt is crystallized at a temperature ranging from Tc to Tg, wherein Tc is the temperature of crystallization initiation of the lactic acid-based polymer composition and Tg is the glass transition temperature of the lactic acid-based polymer composition measured by a differential scanning calorimeter.

Here Hereinafter, the present invention will be described in more detail.

amide compounds

The amide compounds represented by the general formula (1) of the present invention can be easily synthesized by conventional methods (eg, a method disclosed in Japanese Unexamined Patent Publication No. 309821-1995) by amidating one represented by the general formula (1a) aliphatic, alicyclic or aromatic polycarboxylic acid: R ⁹ ( COOH) _f (1a) wherein R ^{9 has} the same meaning as described above R ¹ and f has the same meaning as a above, or an anhydride, alkyl ester (especially C _1-4 alkyl ester) or chloride thereof having at least one represented by the general formula (1b) aliphatic, alicyclic or aromatic amide R ¹⁰ -NH ₂ (1b) wherein R ^{10 has} the same meaning as described above R ² can be prepared.

Therefore, the "polycarboxylic acid residue" represented by R ¹ in the general formula (1) is a residue obtained by removing all of the carboxyl groups from an aliphatic, alicyclic or aromatic polycarboxylic acid represented by the general formula (1a) and illustrated below. The number of carbon atoms of R ¹ refers to the number of carbon atoms having the "polycarboxylic acid residue" (R ⁹ = R ¹ ) obtained by removing the carboxyl groups. R ^{2 of} the general formula (1) is a group obtained by removing the amino group from an aliphatic, alicyclic or aromatic monoamine represented by the general formula (1b) and illustrated below.

Examples of the aliphatic polycarboxylic acids are aliphatic carboxylic acids represented by the general formula (1a), wherein R ^{9 has} 2 to 30, especially 4 to 10, carbon atoms and 2 to 6 (especially 2 to 4) carboxyl groups. Examples include diphenylmalonic, succinic, phenylsuccinic, diphenylsuccinic, glutaric, 3,3-dimethylglutaric, adipic, pimelic, suberic, azelaic, sebacic, 1,2-dodecanedicarboxylic, 1,14-tetradecanedicarboxylic, 1,18-octadecanedicarboxylic, citric, methanetricarboxylic, Tricarballylic acid, propenecarboxylic acid, pentanetricarboxylic acid, ethane tetracarboxylic acid, propane tetracarboxylic acid, pentanetetracarboxylic acid, pentanetetracarboxylic acid, butanetetracarboxylic acid (in particular 1,2,3,4-butanetetracarboxylic acid), dodecantetracarboxylic acid, pentane pentacarboxylic acid, tetradecanhexacarboxylic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylene glycol bis (β-aminoethyl ether) -N, N, N ', N'-tetraacetic acid, diethylenetriaminepentaacetic acid, N -hydroxylethylethylenediamine-N, N', N'-triacetic acid, 1,3-diaminopropan-2-ol-N, N, N ', N'-tetraacetic acid, 1,2- Diaminopropane-N, N, N ', N'-tetraacetic acid, triethylenetetramine hexaacetic acid, Nitrile tripropionic acid, 1,6-hexanediaminetetraacetic acid, N- (2-carboxyethyl) iminodiacetic acid, etc.

Examples of alicyclic polycarboxylic acids are those represented by the general formula (1a) wherein R ^{9 has} 4-28, especially 5-10, carbon atoms and has 2-6 (especially 2-4) carboxyl groups. Examples include 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, 1,5-decalindicarboxylic acid, 2,6-decalindicarboxylic acid, 4,4'-bicyclohexanedicarboxylic acid, cyclohexanetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, 5 - (succinic acid) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, bicyclo [2.2.2] octa-7-ene-2,3,5,6-tetracarboxylic acid, cyclohexanehexacarboxylic acid, 5,6,9,10 Tetracarboxytricyclo [6.2.2.0 ^2,7 ] dodeca-2,11-diene and lower alkyl substitution products thereof (eg, those substituted with methyl at position 3, 8, 11 or 12), 1,2-cyclohexanediaminetetraacetic acid, 2 , 3,5-Tricarboxycyclopentylacetic acid, 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid, 3,5,6-tricarboxynorbornane-2-acetic acid, thiobis (norbornane-2,3-dicarboxylic acid), bicyclo [4.2. 0] octane-3,4,7,8-tetracarboxylic acid, 1,1'-bicyclopropane-2,2 ', 3,3'-tetracarboxylic acid, 1,2-bis (2,3-dimethyl-2,3-dicarb oxycyclobutyl) ethane, pyrazine-2,3,5,6-tetracarboxylic acid, tricyclo [4,2,2,0 ^2,5 ] decane-9-ene-3,4,7,8-tetracarboxylic acid, 3,4-dicarboxy 1,2,3,4-tetrahydro-1-naphthalenesuccinic acid and lower alkyl substitution products thereof (eg those substituted with methyl at position 1, 5, 6 or 7), 2,3,4,5,6, 7,12,13-octahydrophenanthrene-3,4,5,6-tetracarboxylic acid, etc.

Examples of the aromatic polycarboxylic acids are those represented by the general formula (1a) wherein R ^{9 has} 6 to 28, especially 6 to 12, carbon atoms and 2 to 6 (particularly 2 to 4) carboxyl groups. Specific examples include p-phenylenediacetic acid, p-phenylenediethanoic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, terephthalic acid, 1,8-naphthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 , 7-naphthalenedicarboxylic acid, diphenic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-binaphthyldicarboxylic acid, bis (3-carboxyphenyl) methane, bis (4-carboxyphenyl) methane, 2,2-bis ( 3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 3,3'-sulfonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 3,3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid, 3,3 ' Carbonyl dibenzoic acid, 4,4'-carbonyl dibenzoic acid, 3,3'-thiodibenzoic acid, 4,4'-thiodibenzoic acid, 4,4 '- (p-phenylenedioxy) dibenzoic acid, 4,4'-isophthaloyl dibenzoic acid, 4,4'-tereph thaloyldibenzoic acid, dithiosalicylic acid, benzenetricarboxylic acid, benzotetracarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, diphenylsulfontetracarboxylic acid (especially 3,3 ', 4,4'-diphenylsulfontetracarboxylic acid), diphenylmethane-tetracarboxylic acid, perylenetetracarboxylic acid, naphthalenetetracarboxylic acid, 4,4'-dinaphthalic acid, benzidine-3,3' dicarboxylic N, N'-tetraacetic acid, diphenylpropane tetracarboxylic acid, anthracentetracarboxylic acid, phthalocyanine tetracarboxylic acid, ethylene glycol trimellitic acid diester, benzene hexacarboxylic acid, glycerol trimellitic acid triester, etc.

Examples of aliphatic monoamines include saturated aliphatic C _1-18 , especially C _4-10 monoamines and C _2-18 unsaturated aliphatic monoamines, especially C _4-10 monoamines, having a carbon-carbon double bond, such as methylamine, ethylamine , Propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-amylamine, tert-amylamine, hexylamine, heptylamine, n-octylamine, 2-ethylhexylamine, tert-octylamine, nonylamine, decylamine , Undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, octadecenylamine, allylamine, etc.

worin R¹¹ C_1-18-Alkyl, C_2-18-Alkenyl, C_1-18-Alkoxyl, C_3-18-Cycloalkyl, Phenyl oder Halogen ist und g eine ganze Zahl von 1 bis 5 ist; und

worin R¹² lineares oder verzweigtes C_1-4-Alkylen ist, R¹³ die gleiche Bedeutung wie vorstehend beschriebenes R¹¹ hat und h eine ganze Zahl von 0 bis 5 ist.Examples of the alicyclic monoamines include C _3-12 alicyclic monoamines, especially C _5-8 monoamines such as cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, etc., as well as compounds represented by the general formula (2 ) or (3) are shown:

wherein R ^{11 is} C _1-18 alkyl, C _2-18 alkenyl, C _1-18 alkoxyl, C _3-18 cycloalkyl, phenyl or halogen, and g is an integer of 1 to 5; and

wherein R ^{12 is} linear or branched C _1-4 alkylene, R ^{13 has} the same meaning as described above R ¹¹ and h is an integer from 0 to 5.

Specific examples for the alicyclic compounds represented by the general formula (2) Monoamines are methylcyclohexylamine, ethylcyclohexylamine, propylcyclohexylamine, Isopropylcyclohexylamine, tert-butylcyclohexylamine, n-butylcyclohexylamine, Isobutylcyclohexylamine, sec-butylcyclohexylamine, n-amylcyclohexylamine, isoamylcyclohexylamine, sec-amyloxyclohexylamine, tert-amylcyclohexylamine, hexylcyclohexylamine, Heptylcyclohexylamine, octylcyclohexylamine, nonylcyclohexylamine, Decylcyclohexylamine, undecylcyclohexylamine, dodecylcyclohexylamine, Cyclohexylcyclohexylamine, phenylcyclohexylamine, dimethylcyclohexylamine, Diethylcyclohexylamine, dipropylcyclohexylamine, diisopropylcyclohexylamine, Di-n-butylcyclohexylamine, di-sec-butylcyclohexylamine, di-tert-butylcyclohexylamine, Di-n-amylcyclohexylamine, di-tert-amylcyclohexylamine, dihexylcyclohexylamine, Trimethylcyclohexylamine, triethylcyclohexylamine, tripropylcyclohexylamine, Triisopropylcyclohexylamine, tri-n-butylcyclohexylamine, tri-sec-butylcyclohexylamine, Tri-tert-butylcyclohexylamine, methoxycyclohexylamine, ethoxycyclohexylamine, Dimethoxycyclohexylamine, diethoxycyclohexylamine, di-n-butoxycyclohexylamine, Di-sec-butoxycyclohexylamine, di-tert-butoxycyclohexylamine, trimethoxycyclohexylamine, Tri-n-butoxycyclohexylamine, chlorocyclohexylamine, dichlorocyclohexylamine, Methylchlorocyclohexylamine, trichlorocyclohexylamine, bromocyclohexylamine, Dibromocyclohexylamine, tribromocyclohexylamine, etc.

Specific examples for alicyclic monoamines represented by the general formula (3) are cyclohexylmethylamine, methylcyclohexylmethylamine, dimethylcyclohexylmethylamine, Trimethylcyclohexylmethylamine, methoxycyclohexylmethylamine, ethoxycyclohexylmethylamine, Dimethoxycyclohexylmethylamine, chlorocyclohexylmethylamine, dichlorocyclohexylmethylamine, α-cyclohexylethylamine, β-cyclohexylethylamine, methoxycyclohexylethylamine, Dimethoxycyclohexylethylamine, chlorocyclohexylethylamine, dichlorocyclohexylethylamine, α-cyclohexylpropylamine, β-cyclohexylpropylamine, γ-cyclohexylpropylamine, Methylcyclohexylpropylamine, etc.

worin R¹⁴ die gleiche Bedeutung wie vorstehend beschriebenes R¹¹ aufweist und i eine ganze Zahl von 1 bis 5 ist, und

worin R¹⁵ und R¹⁶ die gleiche Bedeutung wie R¹² bzw. R¹¹ aufweisen und j eine ganze Zahl von 0 bis 5 ist.Examples of aromatic monoamines include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, etc., as represented by the general formula (4) or (5):

wherein R ^{14 has} the same meaning as R ¹¹ described above, and i is an integer of 1 to 5, and

wherein R ¹⁵ and R ^{16 have} the same meaning as R ¹² and R ¹¹ and j is an integer from 0 to 5.

Specific examples for aromatic monoamines represented by the general formula (4) are toluidine, ethylaniline, propylaniline, cumidine, tert-butylaniline, n-butylaniline, isobutylaniline, sec-butylaniline, n-amylaniline, isoamylaniline, sec-amylaniline, tert-anylaniline, hexylaniline, heptylaniline, octylaniline, Nonylaniline, decylaniline, undecylaniline, dodecylaniline, cyclohexylaniline, Aminodiphenyl, aminostyrene, dimethylaniline, diethylaniline, dipropylaniline, Diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, di-tert-butylaniline, trimethylaniline, Triethylaniline, tripropylaniline, tri-tert-butylaniline, anisidine, ethoxyaniline, Dimethoxyaniline, diethoxyaniline, trimethoxyaniline, tri-n-butoxyaniline, Chloranil, dichloranil, trichloraniline, bromoaniline, dibromaniline, Tribromoaniline, etc.

Specific examples for aromatic monoamines represented by the general formula (5) are benzylamine, methylbenzylamine, dimethylbenzylamine, trimethylbenzylamine, Methoxybenzylamine, ethoxybenzylamine, dimethoxybenzylamine, chlorobenzylamine, Dichlorobenzylamine, α-phenylethylamine, β-phenylethylamine, methoxyphenylethylamine, Dimethoxyphenylethylamine, chlorophenylethylamine, dichlorophenylethylamine, α-phenylpropylamine, β-phenylpropylamine, γ-phenylpropylamine, Methylphenylpropylamine, etc.

Of the above-described amide compounds, preferred are compounds of the general formula (1) wherein R ^{1 is} 1,4-cyclohexanedicarboxylic acid residue, 2,6-naphthalenedicarboxylic acid residue, trimesic acid residue or 1,2,3,4-butanetetracarboxylic acid residue , in particular a trimesic acid radical.

Among them, preferred are compounds of the general formula (1) wherein R ^{1 is} a 1,4-cyclohexanedicarboxylic acid residue, a 2,6-naphthalenedicarboxylic acid residue, a trimesic acid residue or a 1,2,3,4-butanetetracarboxylic acid residue and R ^{2 is} tert-butyl, cyclohexyl, phenyl, 2-methylcyclohexyl, 4-methylcyclohexyl or benzyl.

From the amide compounds represented by the general formula (1) of the present invention are trimesic acid tricyclohexylamide, trimesic acid tri (2-methylcyclohexylamide), Trimesinsäuretri (4-methylcyclohexylamide), 1,4-Cyclohexandicarbonsäuredicyclohexylamid, 1,4-Cyclohexandicarbonsäuredi (2-methylcyclohexylamide), 1,4-Cyclohexandicarbonsäuredibenzylamid, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-Butantetracarbonsäuretetraanilid and appropriate connections especially recommended.

Even though the particle diameter of the amide compounds useful in the invention not limited is, as far as the advantages of the invention are achieved, he is in In view of the dissolution rate or the dispersing power in a molten resin as small as possible. The mean particle diameter, measured by laser diffraction and light scattering method lies usually in the range of 0.1 to 500 μm, preferably 1 to 200 microns and more preferably 1 to 100 μm.

Ester plasticizer

Ester plasticizers, which are useful in the invention are not limited and include e.g. (1) polyhydric alcohol derivatives, (2) hydroxycarboxylic acid derivatives, (3) aliphatic or aromatic carboxylic esters, (4) polyether polyol derivatives, (5) phosphoric acid derivatives etc. Especially preferred are (1) polyhydric alcohol derivatives, (2) hydroxycarboxylic acid derivatives and (4) polyether polyol derivatives. These ester plasticizers can be used alone or used in combination.

<(1) Polyhydric alcohol derivatives>

polyvalent Alcohol derivatives are preferably glycerol derivatives.

Glycerol derivatives are preferably glycerol-aliphatic-acid (aliphatic acid: C _2-18 ) -triesters. Specific examples include glycerol triacetate, glycerol tripropionate, glycerol tricapronate, glycerol tricaprylate, glycerol tri (2-ethylhexanoate), glycerol triisononanoate, glycerol triisosterate, etc.

<(2) Hydroxycarboxylic acid derivatives>

Hydroxycarboxylic acid derivatives are preferably citric acid derivatives. In particular, acetylcitric acid trialkyl (alkyl: C _1-18 ) esters and citric acid trialkyl (alkyl: C _1-18 ) esters are preferred. Typical examples are, in the case of acetyl-citric acid trialkyl (alkyl: C _1-18 ) esters, triethyl acetyl citrate, triisopropyl acetyl citrate, tributyl acetyl citrate, tri (2-ethylhexyl) acetyl citrate, triisononyl acetyl citrate, triisostearyl acetyl citrate; Triethyl citrate, triisopropyl citrate, tributyl citrate, tri (2-ethylhexyl) citrate, triisononyl citrate, triisostearyl citrate, etc.

<(4) Polyetherpolyol Derivatives>

Polyetherpolyol derivatives are preferably polyalkylene glycol derivatives. Examples of polyalkylene glycol derivatives include diesters of polyalkylene glycols and C _2-18 aliphatic carboxylic acids, especially C _6-10 carboxylic acids or C _7-18 aromatic carboxylic acids, especially C _7-14 carboxylic acids, etc.

Examples of the aromatic carboxylic acids are preferably benzoic acid which may contain one or two (especially one) substituent selected from the group consisting of C _1-4 alkyl, halogen, phenyl and hydroxyl. Unsubstituted benzoic acid is more preferable.

Examples for the The above-mentioned polyalkylene glycol include diethylene glycol, Triethylene glycol, tetraethylene glycol, polyethylene glycol (number average molecular weight: 150 to 2,000), dipropylene glycol, tripropylene glycol, Tetrapropylene glycol, polypropylene glycol (number average molecular weight: 150-2000) etc.

Examples of esters include diethylene glycol di-aliphatic carboxylic acid (aliphatic carboxylic acid: C _2-18 ) ester, triethylene glycol di-aliphatic carboxylic acid (aliphatic carboxylic acid: C _2-18 ) ester, tetraethylene glycol di-aliphatic carboxylic acid (aliphatic carboxylic acid: C _{2-) 18} ) ester, polyethylene glycol (number average molecular weight: 150 to 2,000) -di-aliphatic-carboxylic acid (aliphatic carboxylic acid: C _2-18 ) ester, diethylene glycol di-aromatic carboxylic acid ester, triethylene glycol di-aromatic carboxylic acid ester, tetraethylene glycol di-aromatic carboxylic acid ester , Polyethylene glycol (number average molecular weight: 150 to 2,000) -di-aromatic-carboxylic acid ester, dipropylene glycol-di-aliphatic-carboxylic acid (aliphatic carboxylic acid: C _2-18 ) ester, tripropylene glycol di-aliphatic-carboxylic acid (aliphatic carboxylic acid: C _2-18 ) - ester, tetrapropylene glycol di-aliphatic-carboxylic acid (aliphatic carboxylic acid: C _2-18 ) ester, polypropylene glycol (number average el molecular weight: 150 to 2,000) -di-aliphatic-carboxylic acid (aliphatic carboxylic acid: C _2-18 ) ester, tripropylene glycol di-aromatic carboxylic acid ester, tripropylene glycol di-aromatic carboxylic acid ester, tetrapropylene glycol di-aromatic carboxylic ester, polypropylene glycol (number average molecular weight : 150 to 2,000) -di-aromatic-carboxylic acid esters, etc.

Specific examples of polyalkylene glycol derivatives include diethylene glycol diacetate, Diethylenglycoldipropionat, Diethylenglycoldicapronat, Diethylenglycoldicaprylat, diethylene glycol di (2-ethylhexanoate), Diethylenglycoldiisononanoat, Diethylenglycoldiisostearat, triethylene glycol diacetate, Triethylenglycoldipropionat, Triethylenglycoldicapronat, triethylene glycol dicaprylate, triethylene glycol di (2-ethylhexanoate), Triethylenglycoldiisononanoat, Triethylenglycoldiisostearat, Tetraethylenglycoldiacetat, Tetraethylenglycoldipropionat, Tetraetehylenglycoldicapronat , Tetraethylenglycoldicaprylat, tetraethylene glycol di (2-ethylhexanoate), Tetraethylenglycoldiisononanoat, Tetraethylenglycoldiisostearat, Polyethylenglycoldiacetat, Polyethylenglycoldipropionat, Polyethylenglycoldicapronat, Polyethylenglycoldicaprylat, polyethylene glycol di (2-ethylhexanoate), Polyethylenglycoldiisononanoat, Polyethylenglycoldiisostearat, diethylene glycol dibenzoate, Diethylenglycolditoluat, diethylene glycol di (ethylbenzoate), di ethylene glycol di (isopropyl benzoate), diethylene glycol di (tert-butyl benzoate, diethylene glycol di (chlorobenzoate), diethylene glycol di (hydroxybenzoate), diethylene glycol di (phenyl benzoate), triethylene glycol dibenzoate, triethylene glycol di-toluate, triethylene glycol di (ethyl benzoate), triethylene glycol di (isopropyl benzoate), triethylene glycol di (tert-butyl benzoate), triethylene glycol diol (chlorobenzoate), triethylene glycol di (hydroxybenzoate), triethylene glycol di (phenylbenzoate), tetraethylene glycol dibenzoate; Tetraethylene glycol ditalate, tetraethylene glycol di (ethyl benzoate), tetraethylene glycol di (isopropyl benzoate), tetraethylene glycol di (tert-butyl benzoate), tetraethyl glycol di (chlorobenzoate), tetraethylene glycol di (hydroxybenzoate), tetraethylene glycol di (phenylbenzoate), polyethylene glycol dibenzoate, polyethylene glycol di-toluate, polyethylene glycol di (ethyl benzoate), polyethylene glycol di (isopropyl benzoate), polyethylene glycol di (tert-butyl benzoate), polyethylene glycol di (chlorobenzoate), polyethylene glycol di (hydroxyl benzoate), polyethylene glycol di (phenyl benzoate ) Dipropylenglycoldiacetat, Dipropylenglycoldipropionat, Dipropylenglycoldicapronat, Dipropylenglycoldicaprylat, dipropylene glycol di (2-ethylhexanoate), Dipropylenglycoldiisononanoat, Dipropylenglycoldiisostearat, Tripropylenglycoldiacetat, Tripropylenglycoldipropionat, Tripropylenglycoldicapronat, Tripropylenglycoldicaprylat, tripropylene glycol di (2-ethylhexanoate), Tripropylenglycoldiisononanoat, Tripropylenglycoldiisostearat, tetrapropylene glycol diacetate, Tetrapropylenglycoldipropionat, Tetrapropylenglycoldicapronat, Tetrapropylenglycoldicaprylat, tetrapropylene (2-ethylhexanoate), tetrapropylene glycol diisononan oat, Tetrapropylenglycoldiisostearat, Polypropylenglycoldiacetat, Polypropylenglycoldipropionat, Polypropylenglycoldicapronat, Polypropylenglycoldicaprylat, polypropylene glycol di (2-ethylhexanoate), Polypropylenglycoldiisononanoat, Polypropylenglycoldiisostearat, Dipropylenglycoldibenzonat, Dipropylenglycolditoluat, dipropylene glycol di (ethylbenzoate), dipropylene glycol di (isopropyl benzoate), dipropylene glycol di (t-butylbenzoate), dipropylene glycol di (chlorobenzoate), dipropylene glycol di (hydroxylbenzoate), dipropylene glycol di (phenylbenzoate), tripropylene glycol dibenzoate, Tripropylenglycolditoluat, tripropylene glycol di (ethylbenzoate), tripropylene glycol di (isopropyl benzoate), tripropylene glycol di (t-butylbenzoate), tripropylene glycol di (chlorobenzoate), tripropylene glycol di (hydroxybenzoate), tripropylene glycol di (phenylbenzoate), Tetrapropylenglycoldibenzoat, Tetrapropylenglycolditoluat , Tetrapropylene glycol di (ethyl benzoate), tetrapropylene glycol di (isopropyl benzoate), tetrapropylene glycol di (tert-butyl benzoate), tetraprop ylenglycoldi (chlorobenzoate), tetrapropylene (hydroxybenzoate), tetrapropylene (phenylbenzoate), polypropylene glycol, Polypropylenglycolditoluat, polypropylene glycol di (ethylbenzoate), polypropylene glycol di (isopropyl benzoate), polypropylene glycol di (t-butylbenzoate), polypropylene glycol di (chlorobenzoate), polypropylene glycol di (hydroxybenzoate), polypropylene glycol di (phenylbenzoate ), Etc.

<(3) Aliphatic or aromatic carboxylic esters>

Examples for aliphatic or aromatic carboxylic esters include butyl oleate, butyl isostearate and corresponding monocarboxylic acid esters; Di-2-ethylhexyl phthalate, diisononyl phthalate and corresponding phthalic acid esters (Monoester and diester), adipic acid ester (Monoesters and diesters), e.g. Isobutyl adipate, di-2-ethylhexyl adipate etc.; and those mono- and diesters which are produced using sebacin or azelaic acid instead of adipic acid getting produced.

<(5) phosphoric acid derivatives>

Examples of phosphoric acid derivatives include tri (C _1-12 alkyl) phosphates and tri (C _6-12 aryl) phosphates such as tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.

Polymers based on lactic acid

Examples for polymers based on lactic acid, which are the main component of the invention include (a) Lactic acid homopolymers; (b) lactic acid copolymers; (c) polymer blends, which is selected by mixing at least one element the group consisting of lactic acid homopolymers and lactic acid polymers be prepared with other polymers; etc. While the starting materials for this Lactic acid-based polymers, i.e. the lactic acid components, not limited are, are L-lactic acid, D-lactic acid, DL-lactic acid or mixtures thereof or cyclic lactic acid dimers, such as L-lactide, D-lactide, meso-lactide or mixtures thereof, useful.

Even though The relationship of L-lactic acid to D-lactic acid (L / D) not limited is, is lactic acid of high optical purity is preferred to a high melting point to obtain. In particular, it is preferred that the lactic acid is L-lactic acid in a Amount of 80 mol% or more, especially 95 mol% or more, relative to the total lactic acid contains. It is also preferable that the lactide is L-lactide in an amount of 80 mol% or more, and more preferably 95 mol% or more, relative to the total lactide. Among the lactic acid-based polymers can Lactic acid homopolymers and lactic acid copolymers have a weight average molecular weight, which is not limited but suitably selected from a wide range can. Usually is the weight average molecular weight is 50,000 or more, more preferably 50,000 to 500,000 and more preferably 100,000 to 500,000.

<Lactic acid homopolymers>

Examples of lactic acid homopolymers useful in the invention include polymers, which are prepared by subjecting L-lactic acid, D-lactic acid, DL-lactic acid or mixtures thereof directly to a dehydrating condensation or by subjecting cyclic dimers of lactic acid such as L-lactide, D-lactide, meso-lactide or mixtures thereof ring-opening polymerization.

<Lactic acid copolymers>

Lactic acid copolymers are randomly distributed copolymers or block copolymers of the above Lactic acid monomers, Lactides or lactic acid homopolymers and other components copolymerizable therewith. Although usable Lactic acid homopolymers selected from a wide range can be to lactic acid copolymers In this case it is expedient to prepare those with a weight average of the molecular weight of about 1,000 to about 200,000 and preferred to use about 5,000 to about 100,000.

Examples for the above-mentioned other copolymerizable components Compounds with two or more ester linkages functional Groups per molecule, such as (a) dicarboxylic acids, (b) polyhydric alcohols, (c) hydroxycarboxylic acids other than lactic acid, (d) Lactones; and (e) polyesters, polyethers, polycarbonates, etc. made from the components (a) to (d) are produced.

Specific examples of (a) dicarboxylic acids are linear or branched saturated or unsaturated C _4-50 aliphatic _dicarboxylic acids, especially C _4-20 dicarboxylic acids, C _8-20 aromatic dicarboxylic acids and polyether dicarboxylic acids having a number average molecular weight of 2,000 or less, and especially 1,000 or less. Preferred aliphatic dicarboxylic acids are succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid and corresponding linear aliphatic C _4-20 dicarboxylic acids. Preferred aromatic dicarboxylic acids are phthalic acid, terephthalic acid, isophthalic acid, etc.

Prefers as polyether dicarboxylic acids are those with a carboxymethyl group at both terminals of a Polyalkylene ethers, such as polyethylene glycol, polypropylene glycol, polybutylene glycol, Polyethylenpolypropylenglycol etc. Of these are polyether dicarboxylic acids with a number average molecular weight of 2,000 or less, more preferably 1,000 or less, and more preferably 178 to 1,000 prefers.

Examples of (b) polyhydric alcohols are aliphatic polyols, aromatic polyhydric alcohols and polyalkylene ethers. Examples of aliphatic polyols are C _2-50 aliphatic polyols, especially C _2-20 polyols having 2 to 4 hydroxyl groups such as butanediol, hexanediol, octanediol, decanediol, 1,4-cyclohexanedimethanol, glycerin, sorbitan, trimethylolpropane, neopentyl glycol, etc ,

Examples of aromatic polyhydric alcohols are aromatic C _6-20 diols, such as bis (ortho, meta or para) hydroxymethylbenzene, hydroquinone, etc., and aromatic diols having a number average molecular weight of 2,000 or less, especially less than 1,000, and prepared by adding C _2-4 alkylene oxides, in particular ethylene oxide, propylene oxide or butylene oxide, to bisphenol A, bisphenol F or corresponding bisphenols.

Examples for polyalkylene ethers are ether glycols with a number average molecular weight of 2,000 or less, especially 1,000 or less, such as ethylene glycol, Propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, Polypropylene glycol, etc.

Examples of (c) hydroxycarboxylic acids other than lactic acid are C _3-10 hydroxycarboxylic acids (provided that lactic acid is not included), such as glycolic acid, hydroxybutyric acid, 6-hydroxycaproic acid, etc.

Examples for (d) Lactones include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, Pivalolactone, δ-valerolactone etc.

Examples for (e) Polyesters, polyethers and polycarbonates are not limited, provided that they have hitherto been used in the production of lactic acid copolymers are. It is recommended to use those that have a weight-average the molecular weight of 1,000 to 150,000, preferably 5,000 to 100,000.

Of the above-mentioned polyesters, polyethers and polycarbonates, particularly preferred are those prepared by using a polyester as a comonomer. Examples of polyesters suitable as such comonomers are preferably aliphatic polyesters of aliphatic dicarboxylic acid acids (e-1) and aliphatic diols (e-2).

Preferred examples of aliphatic dicarboxylic acids (e-1) which are useful as a component of the above-mentioned aliphatic polyesters are C _4-20 linear aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, etc. Those having side chains and double bonds may also be used be used.

Examples of aliphatic diols (e-2) which are useful as the other component for the aforementioned aliphatic polyesters are C _2-20 aliphatic diols such as ethylene glycol, propanediol, butanediol, hexanediol, octanediol, etc .; Polyalkylene ethers (homopolymers and copolymers) such as polyethylene glycol, polypropylene glycol, polybutylene glycol, etc .; and polyalkylene carbonates. Polyalkylene ethers and polyalkylene carbonates having a number average molecular weight of 2,000 or less, and more preferably 1,000 or less, are preferred.

Next these aliphatic dicarboxylic acids and aliphatic diols also hydroxycarboxylic acids, like lactic acid, glycolic and hydroxybutyric acid; Lactones such as butyrolactone and ε-caprolactone; aromatic dicarboxylic acids; and corresponding compounds having one or more functional Groups that have an ester linkage can form as a secondary Component of the above-described aliphatic polyester used provided that the effect of the invention is not impaired. Of the above-described lactic acid copolymers are copolymers of lactic acid and (c) hydroxycarboxylic acids (of lactic acid different); Copolymers of lactic acid / diols / dicarboxylic acids (in particular Copolymers of aliphatic diols (e-2) and aliphatic dicarboxylic acids (e-1), as described above; and copolymers of lactic acid and (d) lactones; etc. particularly preferred.

at the lactic acid copolymer used here is the proportion of the abovementioned comonomer components (a) bis (e) preferably less than 50% by weight of the total weight of the polymer based on lactic acid, the lactic acid as the main comonomer. When the proportion of the comonomer components (a) to (e) is excessive, become the crystallinity and the heat resistance of the lactic acid-based polymer, and therefore, the proportion of the comonomer components may be appropriately determined according to the purpose and the application selected become. It is recommended that the amount of comonomer components is preferred 1 to 30 wt .-% and more preferably 5 to 20 wt .-%, based on the Total weight of the lactic acid-based polymer.

<Polymer blends>

polymer blends contain as the main component at least one element selected from the group consisting of the aforementioned lactic acid homopolymers and Lactic acid copolymers and as additional polymeric constituent a polyester, such as an aliphatic polyester, aromatic polyester or a mixture thereof. As additional polymeric ingredient is an aliphatic polyester in terms preferred for biodegradability.

Even though the proportion of additional contained Polymer component according to the purpose and the application can be suitably selected, it is preferred Polyester in a proportion of 5 to 50 wt .-% relative to 95 bis 50% by weight of the at least an item selected from the group consisting of lactic acid homopolymers and lactic acid copolymers as described above. If the proportion of the polyester is less than 5% by weight, it is unlikely that flexibility and impact resistance will be achieved become. If it is more than 50% by weight, it is likely that the mechanical properties are not sufficient and transparency is reached. It is more preferable that polyester in one portion from 6 to 40% by weight relative to 94 to 60% by weight of the at least one Elements selected from the group consisting of lactic acid homopolymers and lactic acid copolymers is recorded.

An overly low one Molecular weight of the polyester contained in the polymer blends, leads to insufficient mechanical properties and is therefore not preferred. It's ordinary preferably, polyester having a weight average molecular weight of 10,000 or more, more preferably 30,000 or more, and more preferably To use 50,000 or more. Those with a weight average of Molecular weight of 50,000 to 300,000 are most common used.

Preferred examples of aliphatic dicarboxylic acids useful as a component of the aliphatic polyesters are C _4-20 linear aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacin acid, decanedicarboxylic acid, etc. It is also possible to use those with side chains and / or double bonds.

Examples of aliphatic diols which are suitable as the other component of the aliphatic polyesters are C _2-20 aliphatic diols such as ethylene glycol, propanediol, butanediol, hexanediol, octanediol, etc .; Polyalkylene ethers (homopolymers and copolymers) such as polyethylene glycol, polypropylene glycol, polybutylene glycol, etc .; and polyalkylene carbonates. Polyalkylene ethers and polyalkylene carbonates having a number average molecular weight of 2,000 or less, and more preferably 1,000 or less, are preferred.

Next these aliphatic dicarboxylic acids and aliphatic diols Hydroxycarboxylic acids, such as Lactic acid, glycolic and hydroxybutyric acid; Lactones such as butyrolactone and ε-caprolactone; aromatic dicarboxylic acids; and corresponding compounds having one or more functional Groups, the ester linkages can form also as a secondary Component of the aliphatic polyesters described above can be used, provided that the effect of the invention is not impaired.

<Process for the preparation of polymers based on lactic acid>

The Lactic acid-based polymers, the main ingredient of the invention can be prepared according to conventional methods become. In particular, you can Lactic acid homopolymers by subjecting a lactic acid monomer direct dehydration condensation or by subjection a lactide, i. a cyclic dimer of lactic acid, a ring-opening polymerization (e.g., unchecked JP Patent Publication No. 33861-1995 and 96123-1984).

method for the preparation, purification and polymerization of lactides disclosed in the literature as disclosed in US Patent No. 4057537; in the European Patent Publication No. 261572; in Polymer Bulletin, 14 (1985): 491-495; Makromol. Chem. 1987 (1986): 1611-1628; Etc.

If a copolymer of lactic acid and (c) hydroxycarboxylic acid or a copolymer of lactic acid and (d) lactone is used as a lactic acid-based polymer, include examples of Process for producing such a copolymer subjecting of lactic acid and (c) hydroxycarboxylic acid direct dehydrating polycondensation or subjugation a cyclic dimer of lactic acid (lactide) and (d) lactone a ring-opening polymerization, optionally in the presence of an aliphatic metal salt, such as tin dicapronate or the like as a catalyst (e.g., Japanese Unexamined Patent Publication No. 306264-1994 and U.S. Patent No. 4057537).

If a lactic acid / diol / dicarboxylic acid copolymer as a lactic acid-based polymer are used, include examples of methods of preparation of such a copolymer, the reaction of a cyclic dimer of lactic acid with a polyester polymer of the aliphatic dicarboxylic acid component (e-1) and the diol component (e-2) in any proportions in Presence of a ring-opening polymerization catalyst (e.g., unchecked JP Patent Publication No. 173266-1995); the reaction of (i) a lactic acid homopolymer with (ii) a Polyester of an aliphatic dicarboxylic acid component (e-1) and an aliphatic Diol component (e-2) in the presence of an organic solvent (e.g., EP-A2 0712880) and corresponding methods.

In Polymer mixtures suitable for the invention can be obtained by mixing at least of an item from the group consisting of the aforementioned lactic acid homopolymers and lactic acid copolymers with the one or more additional polymeric ingredients mentioned above according to usual Process are produced. Mixing methods are not limited. The Mixture may e.g. by known methods, such as mechanical stirring Polymers in molten or solution state or mixing the polymers in the form of powders or particles and Melting or dissolving, accomplished become. The polymer blends described above can in particular made using extruders, reactors, rolls, etc. become.

polymer compositions on lactic acid basis

The Lactic acid-based polymer composition of the present invention contains the aforementioned amic acid compound, an ester plasticizer, a lactic acid-based polymer and, if desired, other additives.

The amount of the amide compound to be added is 0.01 to 10 parts by weight, preferably 0.05 to 5 Parts by weight, and more preferably 0.1 to 1 part by weight per 100 parts by weight of the lactic acid-based polymer. If it is less than 0.01 part by weight, the effectiveness as a clarifying agent is usually insufficient. On the other hand, when the amount is more than 10 parts by weight, a part of the amide compound remains undissolved or coagulated in the molten resin, thereby impairing the transparency of the molded article. The amide compound can be used singly or in combination.

The The amount of ester plasticizer to be contained is 1 to 300 parts by weight, preferably 1 to 100 parts by weight, and more preferably 1 to 50 parts by weight per 100 Parts by weight of the lactic acid-based polymer. If she is less is 1 part by weight, the effectiveness as a crystallization improver is usually insufficient. On the other hand, if it is more than 300 parts by weight, it bleeds the plasticizer is likely to be from the surface of the molded article produced and the properties of the object are impaired over time. Although the ester plasticizer to be incorporated in the lactic acid-based polymer usually Can be used individually, a mixture of 2 or more of them can be used if desired is.

method for mixing the amide compound and the ester plasticizer with the Lactic acid-based polymer are not limited and known kneading devices, usually on this technical Area can be used be used. For example, using a Henschel mixer, a ribbon blender, an extruder, a reactor, a kneader, a roller, etc., or a combination of these devices of each starting material in are mixed in a solid form and further mixed with melting and kneaded. This mixture and this kneading usually becomes 120 up to 250 ° C and preferably at 150 to 200 ° C carried out. The lactic acid-based polymer composition of the invention becomes usually produced in the form of pellets.

In addition, to improve various properties such as crystallization rate, heat resistance, mechanical properties, lubricity, etc., inorganic additives such as talc, kaolinite, SiO ₂ , clay, etc. may be added to the lactic acid-based polymer composition of the invention as required, provided that the transparency of the produced Object is not affected. For example, (i) SiO ₂ or the like having a particle diameter of 1 to 50 nm is preferable for improving the lubricity because it does not affect the transparency; and (ii) for accelerating the crystallization during the molding process, a crystalline inorganic substance containing an SiO ₂ component in an amount of at least 10 wt% may be used. Specific examples of such inorganic substances are Talc TM-30 (manufactured by Fuji Talc), kaolin JP-100 (manufactured by Tsuchiya Kaolin), NN kaolin clay (manufactured by Tsuchiya Kaolin), kaolinite ASP-170 (manufactured by Fuji Talc), Kaolin UW (manufactured by Engelhard Corporation), Talc RF (manufactured by Fuji Talc), etc.

The Amount of these inorganic additives not limited, provided the transparency of the moldings not impaired becomes. The amount is ordinary preferably 30% by weight or less, more preferably 20% by weight or less and more preferably 10% by weight or less, more preferably 5 wt% or less, and most preferably 1 wt% or less per 100 parts by weight of the lactic acid-based polymer. In addition, pigments, Stabilizers, antistatic agents, ultraviolet absorbers, Antioxidants, flame retardants, mold release agents, lubricants, Dyes, bactericides, elastomers, fillers, etc. expediently as other additives according to the purpose and the application can be used unless the transparency of the molded article impaired becomes.

Shaped body of invention

Objects that by molding the lactic acid-based polymer composition of the invention as obtained above good biodegradability and excellent transparency and crystallinity (heat resistance) on.

The Forming methods are not limited. Various molding methods commonly used for common plastics such as extrusion, injection molding, vacuum forming, die-cutting etc., can be used become.

<Crystallization>

Processes for crystallizing moldings during or after forming the lactic acid-based polymer composition include, for example, during the molding (1), introducing the lactic acid-based molten polymer composition into a mold and crystallizing therein; (2) the Ex triturating the molten lactic acid-based polymer composition from a T-die extruder and crystallizing through a chill roll (hereinafter, processes (1) and (2) are referred to as "one-step crystallization processes"); and (3) amorphous heat-treating or partially crystalline molded articles prepared by molding the lactic acid-based polymer composition (hereinafter referred to as "two-stage crystallization process"). In the mentioned single-stage crystallization process and the two-stage crystallization process, the optimal temperature conditions to be used are different in the crystallization of the moldings.

at the one-step crystallization processes are the temperature conditions for the Crystallization preferably in the temperature range of the temperature the onset of crystallization of the lactic acid-based polymer composition (hereinafter referred to as "Tc") for Glass transition temperature (hereinafter referred to as "Tg") measured by differential scanning calorimetry (hereinafter referred to as "DSC analysis"). at higher Temperatures as Tc, the crystallization rate is significantly reduced what an impaired Productivity, operability and lack of crystallization leads; why the desired moldings maybe not received. On the other hand, when the temperatures get smaller are Tg, the rate of crystallization becomes excessively low, with the result that the desired moldings maybe not made. In this method varies the duration of crystallization depending on the type of composition and is not limited if they last longer is considered the time required for adequate crystallization of the shaped bodies.

at The two-stage crystallization process are the to be set Temperature conditions for crystallization preferably in the range of Melting point (hereinafter referred to as "Tm") the lactic acid-based polymer composition (pellets) through to Tg, more preferably (Tg + 5 ° C) to (Tm - 20 ° C), more preferably from (Tg + 10 ° C) to (Tm - 40 ° C). At higher temperatures as a TM, transparency may be impaired even if the moldings be crystallized in a short time, or the shape may be deformed. When the moldings over a heated for a long time can, can they melt. At temperatures lower than Tg, the crystallization rate becomes on the other hand, excessively low and the desired ones crystalline shaped body can maybe not made. In this method varies the duration of the heat treatment dependent on on the type of composition and is not limited, provided longer is considered the time required for sufficient crystallization the molded body.

There but the molding cycle of the two-stage crystallization process longer is one of the one-step crystallization process, it needs not always an industrially satisfactory process.

Shaped body with high transparency and crystallinity can be obtained from the polymer composition on lactic acid basis the invention not only using the single-stage crystallization process, the one superior Can provide a molding cycle, be prepared in an effective manner, but also using of the two-stage crystallization process.

It It is believed that the crystallization mechanism in the present Invention as described below: When the molten Lactic acid-based polymer composition is cooled, the amide compound that is in the polymer composition acts on Lactic acid-based contained as a crystallization seed and the lactic acid-based polymer crystallized as small crystals, creating a transparent, highly crystalline shaped body is prepared, and it is believed that the amide compound as a clarifying agent serves. It is further believed that the ester plasticizer the Function of increase the rate of crystallization, especially the rate of crystallization the lactic acid-based polymer, has, whereby the molding cycle of the molding is shortened.

In In this description, Tg refers to the glass transition start temperature (Tg), in which the lactic acid-based polymer composition (pellets) is rubbery and Tm refers to the peak peak temperature of the melt peak (Melting point: Tm) measured by DSC analysis, wherein the polymer composition on lactic acid basis (Pellets) is heated at a rate of 10 ° C / min. Tc refers to the temperature of the onset of crystallization of the polymer composition based on lactic acid, measured by a DSC analysis, in which the melt of the polymer lactic acid-based a speed of 10 ° C / min chilled becomes.

• a) Beim Spritzgießen kann der gewünschte Formkörper, der sowohl Transparenz als auch Kristallinität aufweist, gemäß einem einstufigen Kristallisationsverfahren erhalten werden, z.B. durch Einleiten einer Schmelze der Polymerzusammensetzung auf Milchsäurebasis (Pellets) enthaltend eine Amidverbindung, einen Ester-Weichmacher und ein Polymer auf Milchsäurebasis in ein Formwerkzeug, das bei einer Temperatur zwischen Tc und Tg gehalten wird. Außerdem kann der gewünschte Formkörper, der sowohl Transparenz als auch Kristallinität aufweist, gemäß einem zweistufigen Kristallisationsverfahren erhalten werden, z.B. durch Einleiten einer Schmelze derartiger Pellets in ein Formwerkzeug, das bei einer geringeren Temperatur als Tg gehalten wird, und Halten des so erhaltenen amorphen oder teilweise kristallisierten Formkörpers in einer Atmosphäre mit einer Temperatur im Bereich von Tg bis Tm oder durch Inkontaktbringen des Formkörpers mit einem Heizmedium.
• b) Beim Strangpressen kann die gewünschte Platte oder Folie, die sowohl Transparenz als auch Kristallinität aufweist, nach einem einstufigen Kristallisationsverfahren erhalten werden, z.B. durch Extrudieren einer Schmelze von derartigen Pellets auf eine Kühlwalze, die bei einer Temperatur im Bereich von Tc bis Tg gehalten wird, durch einen üblicherweise eingesetzten T-Düsen-Extruder und Kristallisieren des sich ergebenden Produkts auf der Kühlwalze. Überdies wird eine amorphe oder teilweise kristallisierte Folie oder Platte, die durch Extrudieren der Pellets durch einen gewöhnlich eingesetzten T-Düsen-Extruder, auf eine Kühlwalze, die bei einer Temperatur unter der von Tg gehalten wird, hergestellt wird durch Hindurchleiten durch einen Ofen (Heizofen) oder heißes Wasser, die bei einer Temperatur zwischen Tg und Tm gehalten werden, kontinuierlich wärmebehandelt oder chargenweise wärmebehandelt. Dadurch kann die gewünschte Folie oder Platte, die sowohl Transparenz als auch Kristallinität aufweisen, auch nach einem zweistufigen Kristallisationsverfahren hergestellt werden.

Hereinafter, typical processes for producing articles capable of giving the molded articles transparency and crystallinity at the same time will be described.

• a) In injection molding, the desired shaped body, which has both transparency and crystallinity, can be obtained according to a one-step crystallization process, for example by introducing a A melt of the lactic acid-based polymer composition (pellets) containing an amide compound, an ester plasticizer and a lactic acid-based polymer in a mold held at a temperature between Tc and Tg. In addition, the desired molded article having both transparency and crystallinity can be obtained according to a two-stage crystallization method, for example, by introducing a melt of such pellets into a mold kept at a lower temperature than Tg and holding the amorphous or partially obtained crystallized shaped body in an atmosphere having a temperature in the range of Tg to Tm or by contacting the shaped body with a heating medium.
• b) In extrusion molding, the desired sheet or film having both transparency and crystallinity can be obtained by a one step crystallization process, for example by extruding a melt of such pellets onto a chill roll maintained at a temperature in the range of Tc to Tg through a commonly used T-die extruder and crystallizing the resulting product on the chill roll. Moreover, an amorphous or partially crystallized film or plate prepared by extruding the pellets through a commonly employed T-die extruder onto a chill roll maintained at a temperature below that of Tg is prepared by passing through an oven (heating furnace ) or hot water kept at a temperature between Tg and Tm are continuously heat-treated or batch-heat-treated. Thereby, the desired film or plate, which have both transparency and crystallinity, can also be produced by a two-stage crystallization process.

Of the moldings from a lactic acid-based polymer The invention has excellent transparency. As a hint on the transparency has a shaped body with a thickness of 0.5 mm a haze of 70% or less, in particular 50% or less and advantageously 30% or less. In addition to the high transparency shows the molding a polymer based on lactic acid a high crystallinity. As an indicator of crystallinity has the shaped body preferably has a degree of crystallization of 30% or more and in particular 40% or more measured with an X-ray diffractometer. The Manufacturing processes described above can be readily molded with a degree of crystallization of 30% or more and a haze of 70% or less at a thickness of 0.5 mm. If the optimum temperature conditions from the above molding conditions selected it is also possible moldings made of lactic acid-based polymer with a crystallinity (Heat resistance) and create transparency, so that the objects with a thickness of 0.5 mm, a haze of 30% or less.

Consequently the invention also provides moldings made of lactic acid-based polymer comprising the above-mentioned lactic acid-based polymer composition (i.e., a composition containing the amide compound, the ester plasticizer, the lactic acid-based polymer and, if necessary, other additives) and with a degree of crystallinity of 30% or more and with a haze of 70% or less, preferably 50% or less, and more preferably 30% or less at a thickness of 0.5 mm.

applications the transparent, crystalline (heat-resistant) biodegradable polymer body on lactic acid basis of the invention include films, plates, tapes, labels, laminates, Fibers, knitwear, textiles, nonwovens, papers, felts, cardboard, Rods, bags, tubes, porous Moldings, Container, Parts and other moldings. The moldings of the present invention to be used in particular for agricultural containers, Multifilaments, tunnel foils, vegetation plates, vegetation nets, Threads for seedlings, Cover sheets, plant pots, Fishing lines, Fishing nets and related agricultural, horticultural and Fish materials; Dish tray, Food wrapping films, Trays, stretch films, shrink films, beverage containers and related food packaging materials; heat insulating materials, Racks, ground supports, water retaining tracks, sandbags and appropriate materials for the Construction and building materials; Packaging for paper diapers and health articles and corresponding sanitary Materials; Food containers Grocery shopping bags, garbage bags, general purpose bags, webs, Ribbons, labels, Shampoo bottles, hair conditioner bottles, cosmetic containers and corresponding various items of the daily needs; and packaging materials, shock absorbing materials, adhesive tapes, threads, casing materials for electrical Home appliances and devices office automation, automotive parts and corresponding industrial materials.

EXAMPLES

A production example, examples and comparative examples are given below to illustrate the invention in more detail, but the scope of the invention is not limited to these examples. "Parts" in the examples are all by weight. The conditions for measuring the Melting point of the amide compounds and the physical properties of the molded articles obtained from the lactic acid-based polymers of the invention are as follows.

1) Melting point of the amide compounds

Of the Melting point of an amide compound refers to the temperature, at the endothermic peak (peak peak) with a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50), when the amide compound was heated at a rate of 10 ° C / min.

2) transparency (haze)

Measured according to JIS K-6714 using a turbidimeter Toyo Seiki Seisaku-sho Ltd.

crystallinity

Test pieces that from shaped bodies were obtained with an X-ray diffractometer (manufactured from Rigaku Corporation, RINT-2100) in the 2θ range from 12 to 28 °. Using the graph thus obtained, the ratio of area of the crystalline peaks to the total area (total area of the crystalline portions and the amorphous portions).

4) tensile test

The Yield strength and elongation were measured according to JIS K-6723.

5) Heat resistance test

O:

keine Verformung festgestellt

Δ:

leichte Verformung festgestellt

X:

eindeutige Verformung festgestellt

Test pieces were placed in a gear oven at a temperature of 80 ° C, the deformation of each of the samples after 24 hours was visually observed and evaluated according to the following three divisions:

O:

no deformation detected

Δ:

slight deformation noted

X:

clear deformation detected

(6) temperature of the beginning crystallization (Tc)

The Temperature of onset of crystallization (Tc) refers to the temperature at which the crystallization peak of the polymer composition on lactic acid basis (Pellets, which in the following examples and comparative examples were prepared) with a differential scanning calorimeter (manufactured by Perkin-Elmer Inc., DSC7) was detected when the polymer composition on lactic acid basis was melted and then cooled at a rate of 10 ° C / min.

(7) Glass transition start temperature (Tg) and melting point (Tm)

The Glass transition temperature (Tg) refers to the temperature at which the polymer compositions on lactic acid basis (Pellets, which in the following examples and comparative examples to be obtained) when heated at a rate of 10 ° C / min became rubbery, and the melting point (Tm) refers to Peak peak temperature using a differential scanning calorimeter (manufactured by Perkin-Elmer Inc., DSC7).

PREPARATION EXAMPLE 1

In a nitrogen atmosphere, 0.03 mol of trimesic acid, 0.099 mol of cyclohexylamine, 0.099 mol of triphenyl phosphite, 10 g of pyridine and 50 g of N-methylpyrrolidone were introduced into a 0.5 liter flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas. Inlet was provided, and the reaction was carried out at 100 ° C for 4 h. The reaction mixture was cooled to room temperature and poured into 500 ml of a 1: 1 isopropyl alcohol / water mixture for re-precipitation. Filtration of the precipitate and drying gave the desired trimesic acid tricyclohexylamide. After the FT-IR analysis, the carboxyl group absorption peak disappeared and the amide group absorption peak (1633 cm ^-1 ) was observed, confirming the formation of trimesic acid tricyclohexylamide.
Melting point: 384 ° C

Examples 1 to 23

A Amide compound and an ester plasticizer shown in Table 1 are and are used in the quantities indicated there with 100 parts by weight of a polylactic acid (weight average molecular weight: 180,000, L-lactic acid / D-lactic acid = 97/3, manufactured by Shimadzu Corporation, trade name: "LACTY") mixed and the The resulting mixture was heated at 200 ° C with an extruder with a Cylinder inside diameter of 20 mm (ratio of length / diameter = 19, manufactured from Toyo Seiki Seisaku-sho Ltd., trade name: "Laboplastomill"). The under nitrogen purge extruded resin composition was cooled by water and pelletized with a pelletizer. The thus obtained Pellets were kept at 50 ° C for 24 h dried in vacuum before being subjected to forming.

The dried pellets were placed in a press set at 200 ° C and melted for 2 minutes, and the melt was pressed at a pressure of 100 kgf / cm ² at 200 ° C for 5 minutes and then crystallized under the conditions described in Table 1, thereby a plate with a thickness of 0.5 mm was prepared by the one-step crystallization process.

One Test piece (thickness: 0.5 mm) was cut from the plate thus obtained. The transparency (Haze), the degree of crystallization, the tensile strength and the heat resistance of the test piece measured. The results are shown in Tables 1 and 2.

COMPARATIVE EXAMPLES 1 UNTIL 5

pellets were prepared in the same manner as in Example 1 except that no amide compounds were used. The pellets thus produced were dried and shaped as in the example and under the table 2 conditions crystallized, which is a plate with a thickness of 0.5 mm. Table 2 shows the results of measured physical properties of the plate thus obtained.

COMPARATIVE EXAMPLES 6 AND 7

pellets were prepared in the same manner as in Example 1 except that no ester plasticizers were used. The pellets thus produced were dried and shaped as in the example and under the table 2 conditions crystallized, which is a plate with a thickness of 0.5 mm. Table 2 shows the results of measured physical properties of the plate thus obtained.

COMPARATIVE EXAMPLES 8 AND 9

pellets were prepared in the same manner as in Example 1 except that neither amide compounds nor ester plasticizers were added. The pellets thus obtained were dried as in the example and crystallized and crystallized under the conditions described in Table 2, which gave a plate with a thickness of 0.5 mm. Table 2 shows the results of the measured physical properties of the thus obtained Plate.

EXAMPLES 24 TO 26

A Amide compound and an ester plasticizer shown in Table 3 are and are used in the quantities indicated there with 100 parts by weight of a polylactic acid (weight average molecular weight: 180,000, L-lactic acid / D-lactic acid = 97/3, manufactured and sold by Shimadzu Corporation, trade name: "LACTY") 200 ° C with an extruder with a cylinder inside diameter of 20 mm (length / diameter: 19, manufactured by Toyo Seiki Seisaku-sho, Ltd., trade name: "Lactoplatomill"). The under nitrogen purge extruded resin composition was cooled by water and pelletized with a pelletizer. The thus obtained Pellets were kept at 50 ° C for 24 h dried in vacuum before being subjected to forming.

The dried pellets were used in an injection molding machine (contact pressure: 40 tons, manufactured by Nissei Plastic Industrial Co., Ltd.) at a Spritzgehäusetemepratur from 160 to 200 ° C, an injection time of 10 s and a mold temperature and cooling time such as Shaped in Table 3, whereby a plate the size of a Business card with thickness ranges of 1 mm and 0.5 mm is obtained.

The Transparency (turbidity) and the degree of crystallinity of the plate thus prepared was measured and the results are shown in Table 3.

COMPARATIVE EXAMPLES 10 AND 11

pellets were prepared in the same manner as in Example 24 except that no amide compounds were used. The pellets thus produced were under the conditions described in Table 3 as in the example dried and shaped, giving a plate of the same size as the produced in this example. Table 3 shows the Results of the measured physical properties of the thus obtained Plate.

COMPARATIVE EXAMPLES 12 AND 13

pellets were prepared in the same manner as in Example 24 except that no ester plasticizers were used. The pellets thus produced were treated with the conditions described in Table 3 as in the example dried and shaped, giving a plate of the same size as the in the example produced plate. Table 3 shows the results the measured physical properties of the plate thus obtained.

COMPARATIVE EXAMPLES 14 AND 15

pellets were prepared in the same manner as in Example 24 except that neither amide compounds nor ester plasticizers were used. The pellets thus prepared were subjected to those described in Table 3 Conditions dried and shaped, giving a plate with the same Size like that the plate prepared in the example gave. Table 13 shows the Results of the measured physical properties of the thus obtained Plate.

In Tables 1 to 3, the letters a to h indicate the type of amide compounds and letters A to K indicate the type of ester plasticizer.

1) amide compounds

• a: trimesic acid tricyclohexylamide (Melting point: 384 ° C)
• b: trimesic acid tri (4-methylcyclohexylamide) (Melting point: 366 ° C)
• c: trimesic acid tri (tert-butylamide) (Melting point: 368 ° C)
• d: 1,4-cyclohexanedicarboxylic acid di (2-methylcyclohexylamide) (Melting point: 363 ° C)
• e: 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide (Melting point: 381 ° C)
• f: 2,6-naphthalic acid dicarboxylic acid dicyclohexylamide (Melting point: 385 ° C)
• g: 1,4-cyclohexanedicarboxylic acid dibenzylamide (Melting point: 310 ° C)
• h: 1,2,3,4-butanetetracarboxylic acid tetraanilide (Melting point: 331 ° C)

2) ester plasticizer

• A: glycerol triacetate
• B: Tributyl acetyl citrate
• C: tri (2-ethylhexyl) citrate
• D: triethylene glycol di (2-ethylhexanoate)
• E: diethylene glycol dibenzoate
• F: Polyethylene glycol (having a number average molecular weight of 300) - di (2-ethylhexanoate)
• G: Polyethylene glycol (having a number average molecular weight from 200) - dibenzoate
• H: tripropylene glycol di (2-ethylhexanoate)
• I: dipropylene glycol dibenzoate
• J: Polypropylene glycol (having a number average molecular weight from 400) -di (2-ethylhexanoate)
• K: Polypropylene glycol (having a number average molecular weight from 400) dibenzoate

With respect to Table 3, 40 seconds of cooling in Comparative Examples 10, 12 and 14 barely crystallized the molded article and the molded articles were soft and difficult to take out of the mold and deformed upon removal, and therefore it was impossible to obtain a molded article in which the haze value could be accurately measured. In Comparative Examples 11, 13 and 15, it was necessary to carry out the cooling for as long as 150 to 300 seconds to give moldings good mold releasability and heat resistance. The transparency of it was bad.

COMMERCIAL APPLICABILITY

According to the present Invention can be a transparent, crystalline (heat-resistant) moldings comprising a lactic acid-based polymer to be provided. According to the present Invention can Transparency and crystallinity an article comprising a lactic acid-based polymer be awarded at the same time.

Further For example, the process for producing a polymeric article can be described Lactic acid-based the invention, the rate of crystallization during the Increase crystallization step and thereby the molding cycle can be shortened.

If a shaped body made of lactic acid-based polymer using the lactic acid-based polymer composition moreover, such a molded article is produced by the present invention excellent mold release.

Claims (15)

A lactic acid-based polymer composition comprising: (i) at least one amide compound represented by the general formula (1): R ¹ - (- CONHR ² ) _a (1) wherein R ^{1 represents} a saturated or unsaturated aliphatic C _2-30 polycarboxylic acid residue, a saturated or unsaturated C _4-28 alicyclic polycarboxylic acid residue or a C _6-28 aromatic polycarboxylic acid residue; R ^{2 is} C _1-18 alkyl, C _2-18 alkenyl, C _3-12 cycloalkyl or cycloalkenyl, phenyl, naphthyl, anthryl or one represented by the general formula (a), the general formula (b), the general Represents formula (c) or the general formula (d) represented group;

wherein R ^{3 is} C _1-18 alkyl, C _2-18 alkenyl, C _1-18 alkoxy, C _3-18 cycloalkyl, phenyl, or halo; R ^{4 is} linear or branched C _1-4 alkylene; R ⁵ and R ^{6 have} the same meaning as R ³ ; R ^{7 has} the same meaning as R ⁴ ; R ^{8 has} the same meaning as R ³ ; a is an integer from 2 to 6; b is an integer from 1 to 5; c is an integer of 0 to 5; d is an integer from 1 to 5; and e is an integer of 0 to 5; (ii) at least one ester plasticizer; and (iii) a lactic acid-based polymer. A lactic acid-based polymer composition according to claim 1, wherein R ^{1 is} a 1,4-cyclohexanedicarb bonsäurerest, a 2,6-Naphthalindicarbonsäurerest, a Trimesinsäurerest or a 1,2,3,4-Butantetracarbonsäurerest. A lactic acid-based polymer composition according to claim 2, wherein R ^{1 is} a trimesic acid residue. A lactic acid-based polymer composition according to claim 2, wherein R ^{2 is} tert-butyl, cyclohexyl, phenyl, 2-methylcyclohexyl, 4-methylcyclohexyl or benzyl. A lactic acid-based polymer composition according to claim 4, wherein the amide compound comprises at least one member selected from the group from trimesic acid tricyclohexylamide, Trimesinsäuretri (2-methylcyclohexylamide), Trimesinsäuretri (4-methylcyclohexylamide), 1,4-Cyclohexandicarbonsäuredicyclohexylamid, 1,4-Cyclohexandicarbonsäuredi (2-methylcyclohexylamide), 1,4-Cyclohexandicarbonsäuredibenzylamid, 2,6-Naphthalindicarbonsäuredicyclohexylamid, 1,2,3,4-Butantetracarbonsäuretetracyclohexylamid and 1,2,3,4-butanetetracarboxylic acid tetraanilide is. A lactic acid-based polymer composition according to claim 1, wherein the ester plasticizer comprises at least one element selected from the group consisting of polyhydric alcohol derivatives, hydroxycarboxylic acid derivatives, aliphatic or aromatic carboxylic acid esters, polyether polyol derivatives and phosphoric acid derivatives is. A lactic acid-based polymer composition according to claim 6, wherein the ester plasticizer comprises at least one element selected from the group consisting of glycerol derivatives, citric acid derivatives and Polyalkylenglycolderivaten is. A lactic acid-based polymer composition according to claim 7, wherein the glycerin derivatives are at least one glycerol tri-C _2-18 aliphatic carboxylic acid ester. Polymer composition based on lactic acid according to claim 7, wherein the citric acid derivatives from Acetylcitronensäuretri-C _1-18 -alkyl and Citronensäuretri-C are at least one element selected from the group consisting _1-18 -alkyl. A lactic acid-based polymer composition according to claim 7, wherein the polyalkylene glycol derivatives are at least one member selected from the group consisting of diethylene glycol di-C _2-18 aliphatic carboxylic acid esters, triethylene glycol di-C _2-18 aliphatic carboxylic acid esters, tetraethylene glycol di-C _2-18 aliphatic carboxylic acid esters, polyethylene glycol di C _2-18 aliphatic carboxylic acid esters, diethylene glycol di-aromatic carboxylic acid esters, triethylene glycol di-aromatic carboxylic acid esters, tetraethylene glycol di-aromatic carboxylic acid esters, polyethylene glycol di-aromatic carboxylic acid esters, dipropylene glycol di-C _2-18 aliphatic-carbonsäureestern, tripropylene glycol-di-C _2-18 aliphatic-carbonsäureestern, tetrapropylene glycol di-C _2-18 aliphatic-carbonsäureestern, polypropylene glycol-di-C _2-18 -aliphatic-carboxylic acid esters, dipropylene glycol-di-aromatic-carboxylic acid esters, tripropylene glycol-di-aromatic-carboxylic acid esters, tetrapropylg lycol-di-aromatic-carboxylic acid esters and polypropylene glycol-di-aromatic-carboxylic acid esters. A lactic acid-based polymer composition according to claim 1, wherein the lactic acid-based polymer has a weight average molecular weight of 50,000 or more. A lactic acid-based polymer composition according to claim 1, which 0.01 to 10 parts by weight of the amide compound and 1 to 300 parts by weight of the ester plasticizer per 100 parts by weight of the lactic acid-based polymer includes. Moldings, prepared by molding the lactic acid-based polymer composition according to any of the claims 1 to 12. moldings according to claim 13, wherein the shaped body has a degree of crystallization of 30% or more, measured with an X-ray diffractometer in the 2θ range of 12 to 28 °, and a transparency corresponding to a haze of 70% or less a thickness of 0.5 mm measured in accordance with JIS K-6714. A process for producing the lactic acid-based polymer molded article according to claim 14, wherein the process comprises: (1) providing the lactic acid-based polymer composition in the form of pellets, filling the Melting the pellets into a mold and crystallizing the melt in the mold; or (2) providing the lactic acid-based polymer composition in the form of pellets, extruding the melt from the pellets from a T-die extruder and crystallizing the melt with a chill roll; wherein the melt is crystallized at a temperature ranging from Tc to Tg, wherein Tc is the temperature of crystallization initiation of the lactic acid-based polymer composition and Tg is the glass transition temperature of the lactic acid-based polymer composition measured by a differential scanning calorimeter.